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Synthesis and Characterization of Octacyano-Fe-Phthalocyanine

[Image: see text] Octacyano-metal-phthalocyanine MPc(CN)(8) is a promising n-type stable organic semiconductor material with eight cyano groups, including a strong electron-withdrawing group at its molecular terminals. However, a thorough investigation of MPc(CN)(8) has not yet been conducted. There...

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Autores principales: Isobe, Momoka, Nakayama, Shota, Takagi, Shunsuke, Araki, Kakeru, Kanai, Kaname
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10399171/
https://www.ncbi.nlm.nih.gov/pubmed/37546620
http://dx.doi.org/10.1021/acsomega.3c02638
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author Isobe, Momoka
Nakayama, Shota
Takagi, Shunsuke
Araki, Kakeru
Kanai, Kaname
author_facet Isobe, Momoka
Nakayama, Shota
Takagi, Shunsuke
Araki, Kakeru
Kanai, Kaname
author_sort Isobe, Momoka
collection PubMed
description [Image: see text] Octacyano-metal-phthalocyanine MPc(CN)(8) is a promising n-type stable organic semiconductor material with eight cyano groups, including a strong electron-withdrawing group at its molecular terminals. However, a thorough investigation of MPc(CN)(8) has not yet been conducted. Therefore, we synthesized FePc(CN)(8) and investigated its crystal structure, chemical and electronic states, electrical properties, photocatalytic activity, and magnetic properties. In this paper, we discuss the various properties of MPc(CN)(8) in comparison with those of FePc. X-ray diffraction measurements indicated that the crystal structure of FePc(CN)(8) was strongly influenced by the cyano groups and differed from the α- and β-forms of FePc. The space group P4/mcc structure of FePc(CN)(8) was similar to that of the x-form of LiPc. The ultraviolet–visible (UV–vis) absorption spectrum of FePc(CN)(8) was observed at wavelengths longer than that of FePc. Density functional theory-based molecular orbital calculations indicated that the energy gap of FePc(CN)(8) is smaller than that of FePc, which can lead to the observation of the Q-band in the UV–vis absorption spectrum of FePc(CN)(8) at longer wavelengths than that of FePc. Because FePc(CN)(8) has a wider optical absorption band in the visible region than FePc, its photocatalytic activity is approximately four times higher than that of FePc. The conductivity of FePc(CN)(8) was also higher than that of FePc, which is due to the larger overlap of π-electron clouds of the molecules in the crystal structure of FePc(CN)(8). Magnetic measurements revealed that FePc(CN)(8) exists in an antiferromagnetic ground state. The magnetic properties of FePc(CN)(8) are specific to its crystal structure, with direct exchange interactions between Fe(2+) ions and π-electron-mediated interactions. In particular, the Pauli paramagnetic behavior at high temperatures and the antiferromagnetic behavior at low temperatures (Weiss temperature θ = −4.3 ± 0.1 K) are characteristic of the π–d system.
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spelling pubmed-103991712023-08-04 Synthesis and Characterization of Octacyano-Fe-Phthalocyanine Isobe, Momoka Nakayama, Shota Takagi, Shunsuke Araki, Kakeru Kanai, Kaname ACS Omega [Image: see text] Octacyano-metal-phthalocyanine MPc(CN)(8) is a promising n-type stable organic semiconductor material with eight cyano groups, including a strong electron-withdrawing group at its molecular terminals. However, a thorough investigation of MPc(CN)(8) has not yet been conducted. Therefore, we synthesized FePc(CN)(8) and investigated its crystal structure, chemical and electronic states, electrical properties, photocatalytic activity, and magnetic properties. In this paper, we discuss the various properties of MPc(CN)(8) in comparison with those of FePc. X-ray diffraction measurements indicated that the crystal structure of FePc(CN)(8) was strongly influenced by the cyano groups and differed from the α- and β-forms of FePc. The space group P4/mcc structure of FePc(CN)(8) was similar to that of the x-form of LiPc. The ultraviolet–visible (UV–vis) absorption spectrum of FePc(CN)(8) was observed at wavelengths longer than that of FePc. Density functional theory-based molecular orbital calculations indicated that the energy gap of FePc(CN)(8) is smaller than that of FePc, which can lead to the observation of the Q-band in the UV–vis absorption spectrum of FePc(CN)(8) at longer wavelengths than that of FePc. Because FePc(CN)(8) has a wider optical absorption band in the visible region than FePc, its photocatalytic activity is approximately four times higher than that of FePc. The conductivity of FePc(CN)(8) was also higher than that of FePc, which is due to the larger overlap of π-electron clouds of the molecules in the crystal structure of FePc(CN)(8). Magnetic measurements revealed that FePc(CN)(8) exists in an antiferromagnetic ground state. The magnetic properties of FePc(CN)(8) are specific to its crystal structure, with direct exchange interactions between Fe(2+) ions and π-electron-mediated interactions. In particular, the Pauli paramagnetic behavior at high temperatures and the antiferromagnetic behavior at low temperatures (Weiss temperature θ = −4.3 ± 0.1 K) are characteristic of the π–d system. American Chemical Society 2023-07-17 /pmc/articles/PMC10399171/ /pubmed/37546620 http://dx.doi.org/10.1021/acsomega.3c02638 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Isobe, Momoka
Nakayama, Shota
Takagi, Shunsuke
Araki, Kakeru
Kanai, Kaname
Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title_full Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title_fullStr Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title_full_unstemmed Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title_short Synthesis and Characterization of Octacyano-Fe-Phthalocyanine
title_sort synthesis and characterization of octacyano-fe-phthalocyanine
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10399171/
https://www.ncbi.nlm.nih.gov/pubmed/37546620
http://dx.doi.org/10.1021/acsomega.3c02638
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